Aqueous dispersions containing of electrically conducting polymers containing high boiling solvent and additives

ABSTRACT

The present invention relates to electrically conductive polymer compositions, and their use in electronic devices. The compositions are an aqueous dispersion of at least one electrically conductive polymer doped with a non-fluorinated polymeric acid, at least one high-boiling polar organic solvent, and an additive selected from the group consisting of fullerenes, carbon nanotubes, and combinations thereof.

RELATED APPLICATION DATA

This application is a division of U.S. application Ser. No. 12/121,121,now allowed, which claims priority under 35 U.S.C. §119(e) from U.S.Provisional Application No. 60/938,786 filed on May 18, 2007, which isincorporated by reference herein in its entirety.

BACKGROUND INFORMATION

1. Field of the Disclosure

This disclosure relates in general to aqueous dispersions ofelectrically conductive polymers containing solvent and additives, andtheir use in electronic devices.

2. Description of the Related Art

Electronic devices define a category of products that include an activelayer. Organic electronic devices have at least one organic activelayer. Such devices convert electrical energy into radiation such aslight emitting diodes, detect signals through electronic processes,convert radiation into electrical energy, such as photovoltaic cells, orinclude one or more organic semiconductor layers.

Organic light-emitting diodes (OLEDs) are an organic electronic devicecomprising an organic layer capable of electroluminescence. OLEDscontaining conducting polymers can have the following configuration:

-   -   anode/buffer layer/EL material/cathode        with additional layers between the electrodes. The anode is        typically any material that has the ability to inject holes into        the EL material, such as, for example, indium/tin oxide (ITO).        The anode is optionally supported on a glass or plastic        substrate. EL materials include fluorescent compounds,        fluorescent and phosphorescent metal complexes, conjugated        polymers, and mixtures thereof. The cathode is typically any        material (such as, e.g., Ca or Ba) that has the ability to        inject electrons into the EL material. Electrically conducting        polymers having low conductivity in the range of 10⁻³ to 10⁻⁷        S/cm are commonly used as the buffer layer in direct contact        with an electrically conductive, inorganic oxide anode such as        ITO.

Electrically conducting polymers which have the ability to carry a highcurrent when subjected to a low electrical voltage, may have utility aselectrodes for electronic devices. However, many conductive polymershave conductivities which are too low for use as electrodes.Furthermore, the mechanical strength of films made from the polymers,either self-standing or on a substrate, may not be sufficient for theelectrode applications.

Accordingly, there is a continuing need for improved conducting polymercompositions.

SUMMARY

There is provided an aqueous dispersion comprising at least oneelectrically conductive polymer doped with at least one non-fluorinatedpolymeric acid polymer, a high-boiling polar solvent, and an additiveselected from the group consisting of carbon fullerenes, nanotubes, andcombinations thereof.

In another embodiment, there is provided a film formed from the abovedispersion.

In another embodiment, electronic devices comprising at least one layercomprising the above film are provided.

BRIEF DESCRIPTION OF THE DRAWINGS

The invention is illustrated by way of example and not limitation in theaccompanying figures.

FIG. 1 is a schematic diagram of an organic electronic device.

Skilled artisans will appreciate that objects in the figures areillustrated for simplicity and clarity and have not necessarily beendrawn to scale. For example, the dimensions of some of the objects inthe figures may be exaggerated relative to other objects to help toimprove understanding of embodiments.

DETAILED DESCRIPTION

There is provided an aqueous dispersion of at least one electricallyconductive polymer doped with at least one non-fluorinated polymericacid, at least one high-boiling polar organic solvent, and an additiveselected from the group consisting of carbon fullerenes, nanotubes, andcombinations thereof. The above dispersion is referred to herein as the“new composition” and the “composite dispersion”.

Many aspects and embodiments are described herein and are merelyexemplary and not limiting. After reading this specification, skilledartisans will appreciate that other aspects and embodiments are possiblewithout departing from the scope of the invention.

Other features and benefits of any one or more of the embodiments willbe apparent from the following detailed description, and from theclaims. The detailed description first addresses Definitions andClarification of Terms followed by the Doped Electrically ConductivePolymer, the Solvent, the Additive, Preparation of the DopedElectrically Conductive Polymer Composition, Buffer Layers, ElectronicDevices, and finally, Examples.

1. Definitions and Clarification of Terms Used in the Specification andClaims

Before addressing details of embodiments described below, some terms aredefined or clarified.

The term “conductor” and its variants are intended to refer to a layermaterial, member, or structure having an electrical property such thatcurrent flows through such layer material, member, or structure withouta substantial drop in potential. The term is intended to includesemiconductors. In some embodiments, a conductor will form a layerhaving a conductivity of at least 10⁻⁷ S/cm.

The term “electrically conductive” as it refers to a material, isintended to mean a material which is inherently or intrinsically capableof electrical conductivity without the addition of carbon black orconductive metal particles.

The term “polymer” is intended to mean a material having at least onerepeating monomeric unit. The term includes homopolymers having only onekind, or species, of monomeric unit, and copolymers having two or moredifferent monomeric units, including copolymers formed from monomericunits of different species.

The term “acid polymer” refers to a polymer having acidic groups.

The term “acidic group” refers to a group capable of ionizing to donatea hydrogen ion to a Brønsted base.

The term “highly-fluorinated” refers to a compound in which at least 90%of the available hydrogens bonded to carbon have been replaced byfluorine.

The terms “fully-fluorinated” and “perfluorinated” are usedinterchangeably and refer to a compound where all of the availablehydrogens bonded to carbon have been replaced by fluorine.

The term “polar” refers to a molecule that has a permanent electricdipole.

The term “high-boiling solvent” refers to an organic compound which is aliquid at room temperature and has a boiling point of greater than 100°C.

The term “doped” as it refers to an electrically conductive polymer, isintended to mean that the electrically conductive polymer has apolymeric counterion to balance the charge on the conductive polymer.

The term “doped conductive polymer” is intended to mean the conductivepolymer and the polymeric counterion that is associated with it.

The term “layer” is used interchangeably with the term “film” and refersto a coating covering a desired area. The term is not limited by size.The area can be as large as an entire device or as small as a specificfunctional area such as the actual visual display, or as small as asingle sub-pixel. Layers and films can be formed by any conventionaldeposition technique, including vapor deposition, liquid deposition(continuous and discontinuous techniques), and thermal transfer.

The term “carbon nanotube” refers to an allotrope of carbon having ananostructure where the length-to-diameter ratio exceeds one million.

The term “fullerene” refers to cage-like, hollow molecules composed ofhexagonal and pentagonal groups of carbon atoms. In some embodiments,there are at least 60 carbon atoms present in the molecule.

The term “nanoparticle” refers to a material having a particle size lessthan 100 nm. In some embodiments, the particle size is less than 10 nm.In some embodiments, the particle size is less than 5 nm.

The term “aqueous” refers to a liquid that has a significant portion ofwater, and in one embodiment it is at least about 40% by weight water;in some embodiments, at least about 60% by weight water.

The term “hole transport” when referring to a layer, material, member,or structure, is intended to mean such layer, material, member, orstructure facilitates migration of positive charges through thethickness of such layer, material, member, or structure with relativeefficiency and small loss of charge.

The term “electron transport” means when referring to a layer, material,member or structure, such a layer, material, member or structure thatpromotes or facilitates migration of negative charges through such alayer, material, member or structure into another layer, material,member or structure.

Although light-emitting materials may also have some charge transportproperties, the terms “hole transport layer, material, member, orstructure” and “electron transport layer, material, member, orstructure” are not intended to include a layer, material, member, orstructure whose primary function is light emission.

The term “organic electronic device” is intended to mean a deviceincluding one or more semiconductor layers or materials. Organicelectronic devices include, but are not limited to: (1) devices thatconvert electrical energy into radiation (e.g., a light-emitting diode,light emitting diode display, diode laser, or lighting panel), (2)devices that detect signals through electronic processes (e.g.,photodetectors photoconductive cells, photoresistors, photoswitches,phototransistors, phototubes, infrared (“IR”) detectors, or biosensors),(3) devices that convert radiation into electrical energy (e.g., aphotovoltaic device or solar cell), and (4) devices that include one ormore electronic components that include one or more organicsemiconductor layers (e.g., a transistor or diode).

As used herein, the terms “comprises,” “comprising,” “includes,”“including,” “has,” “having” or any other variation thereof, areintended to cover a non-exclusive inclusion. For example, a process,method, article, or apparatus that comprises a list of elements is notnecessarily limited to only those elements but may include otherelements not expressly listed or inherent to such process, method,article, or apparatus. Further, unless expressly stated to the contrary,“or” refers to an inclusive or and not to an exclusive or. For example,a condition A or B is satisfied by any one of the following: A is true(or present) and B is false (or not present), A is false (or notpresent) and B is true (or present), and both A and B are true (orpresent).

Also, use of “a” or “an” are employed to describe elements andcomponents described herein. This is done merely for convenience and togive a general sense of the scope of the invention. This descriptionshould be read to include one or at least one and the singular alsoincludes the plural unless it is obvious that it is meant otherwise.

Group numbers corresponding to columns within the Periodic Table of theelements use the “New Notation” convention as seen in the CRC Handbookof Chemistry and Physics, 81^(st) Edition (2000-2001).

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this invention belongs. In the Formulae, the letters Q,R, T, W, X, Y, and Z are used to designate atoms or groups which aredefined within. All other letters are used to designate conventionalatomic symbols. Group numbers corresponding to columns within thePeriodic Table of the elements use the “New Notation” convention as seenin the CRC Handbook of Chemistry and Physics, 81^(st) Edition (2000).

To the extent not described herein, many details regarding specificmaterials, processing acts, and circuits are conventional and may befound in textbooks and other sources within the organic light-emittingdiode display, lighting source, photodetector, photovoltaic, andsemiconductive member arts.

2. Doped Electrically Conductive Polymers

The doped electrically conductive polymer has a polymeric counterionderived from a polymeric acid to balance the charge on the conductivepolymer.

a. Electrically Conductive Polymer

Any electrically conductive polymer can be used in the new composition.In some embodiments, the electrically conductive polymer will form afilm which has a conductivity greater than 0.1 S/cm. In someembodiments, the new compositions described herein can be used to formfilms having a conductivity greater than 100 S/cm.

The conductive polymers suitable for the new composition are made fromat least one monomer which, when polymerized alone, forms anelectrically conductive homopolymer. Such monomers are referred toherein as “conductive precursor monomers.” Monomers which, whenpolymerized alone form homopolymers which are not electricallyconductive, are referred to as “non-conductive precursor monomers.” Theconductive polymer can be a homopolymer or a copolymer. Conductivecopolymers suitable for the new composition can be made from two or moreconductive precursor monomers or from a combination of one or moreconductive precursor monomers and one or more non-conductive precursormonomers.

In some embodiments, the conductive polymer is made from at least oneconductive precursor monomer selected from thiophenes, pyrroles,anilines, and polycyclic aromatics. The term “polycyclic aromatic”refers to compounds having more than one aromatic ring. The rings may bejoined by one or more bonds, or they may be fused together. The term“aromatic ring” is intended to include heteroaromatic rings. A“polycyclic heteroaromatic” compound has at least one heteroaromaticring.

In some embodiments, the conductive polymer is made from at least oneprecursor monomer selected from thiophenes, selenophenes, tellurophenes,pyrroles, anilines, and polycyclic aromatics. The polymers made fromthese monomers are referred to herein as polythiophenes,poly(selenophenes), poly(tellurophenes), polypyrroles, polyanilines, andpolycyclic aromatic polymers, respectively. The term “polycyclicaromatic” refers to compounds having more than one aromatic ring. Therings may be joined by one or more bonds, or they may be fused together.The term “aromatic ring” is intended to include heteroaromatic rings. A“polycyclic heteroaromatic” compound has at least one heteroaromaticring. In some embodiments, the polycyclic aromatic polymers arepoly(thienothiophenes).

In some embodiments, monomers contemplated for use to form theelectrically conductive polymer in the new composition comprise FormulaI below:

wherein:

-   -   Q is selected from the group consisting of S, Se, and Te;    -   R¹ is independently selected so as to be the same or different        at each occurrence and is selected from hydrogen, alkyl,        alkenyl, alkoxy, alkanoyl, alkythio, aryloxy, alkylthioalkyl,        alkylaryl, arylalkyl, amino, alkylamino, dialkylamino, aryl,        alkylsulfinyl, alkoxyalkyl, alkylsulfonyl, arylthio,        arylsulfinyl, alkoxycarbonyl, arylsulfonyl, acrylic acid,        phosphoric acid, phosphonic acid, halogen, nitro, cyano,        hydroxyl, epoxy, silane, siloxane, alcohol, benzyl, carboxylate,        ether, ether carboxylate, amidosulfonate, ether sulfonate, ester        sulfonate, and urethane; or both R¹ groups together may form an        alkylene or alkenylene chain completing a 3, 4, 5, 6, or        7-membered aromatic or alicyclic ring, which ring may optionally        include one or more divalent nitrogen, selenium, tellurium,        sulfur or oxygen atoms.

As used herein, the term “alkyl” refers to a group derived from analiphatic hydrocarbon and includes linear, branched and cyclic groupswhich may be unsubstituted or substituted. The term “heteroalkyl” isintended to mean an alkyl group, wherein one or more of the carbon atomswithin the alkyl group has been replaced by another atom, such asnitrogen, oxygen, sulfur, and the like. The term “alkylene” refers to analkyl group having two points of attachment.

As used herein, the term “alkenyl” refers to a group derived from analiphatic hydrocarbon having at least one carbon-carbon double bond, andincludes linear, branched and cyclic groups which may be unsubstitutedor substituted. The term “heteroalkenyl” is intended to mean an alkenylgroup, wherein one or more of the carbon atoms within the alkenyl grouphas been replaced by another atom, such as nitrogen, oxygen, sulfur, andthe like. The term “alkenylene” refers to an alkenyl group having twopoints of attachment.

As used herein, the following terms for substituent groups refer to theformulae given below:

“alcohol” —R³—OH

“amido” —R³—C(O)N(R⁶)R⁶

“amidosulfonate” —R³—C(O)N(R⁶)R⁴—SO₃Z

“benzyl” —CH₂—C₆H₅

“carboxylate” —R³—C(O)O—Z or —R³—O—C(O)—Z

“ether” —R³—(O—R⁵)_(p)—O—R⁵

“ether carboxylate” —R³—O—R⁴—C(O)O—Z or —R³—O—R⁴—O—C(O)—Z

“ether sulfonate” —R³—O—R⁴—SO₃Z

“ester sulfonate” —R³—O—C(O)—R⁴—SO₃Z

“sulfonimide” —R³—SO₂—NH—SO₂—R⁵

“urethane” —R³—O—C(O)—N(R⁶)₂

-   -   where all “R” groups are the same or different at each        occurrence and:        -   R³ is a single bond or an alkylene group        -   R⁴ is an alkylene group        -   R⁵ is an alkyl group        -   R⁶ is hydrogen or an alkyl group        -   p is 0 or an integer from 1 to 20        -   Z is H, alkali metal, alkaline earth metal, N(R⁵)₄ or R⁵            Any of the above groups may further be unsubstituted or            substituted, and any group may have F substituted for one or            more hydrogens, including perfluorinated groups. In some            embodiments, the alkyl and alkylene groups have from 1-20            carbon atoms.

In some embodiments, in the monomer, both R¹ together form—W—(CY¹Y²)_(m)—W—, where m is 2 or 3, W is O, S, Se, PO, NR⁶, Y¹ is thesame or different at each occurrence and is hydrogen or fluorine, and Y²is the same or different at each occurrence and is selected fromhydrogen, halogen, alkyl, alcohol, amidosulfonate, benzyl, carboxylate,ether, ether carboxylate, ether sulfonate, ester sulfonate, andurethane, where the Y groups may be partially or fully fluorinated. Insome embodiments, all Y are hydrogen. In some embodiments, the polymeris poly(3,4-ethylenedioxythiophene). In some embodiments, at least one Ygroup is not hydrogen. In some embodiments, at least one Y group is asubstituent having F substituted for at least one hydrogen. In someembodiments, at least one Y group is perfluorinated.

In some embodiments, the monomer has Formula I(a):

wherein:

-   -   Q is selected from the group consisting of S, Se, and Te;    -   R⁷ is the same or different at each occurrence and is selected        from hydrogen, alkyl, heteroalkyl, alkenyl, heteroalkenyl,        alcohol, amidosulfonate, benzyl, carboxylate, ether, ether        carboxylate, ether sulfonate, ester sulfonate, and urethane,        with the proviso that at least one R⁷ is not hydrogen, and    -   m is 2 or 3.

In some embodiments of Formula I(a), m is two, one R⁷ is an alkyl groupof more than 5 carbon atoms, and all other R⁷ are hydrogen. In someembodiments of Formula I(a), at least one R⁷ group is fluorinated. Insome embodiments, at least one R⁷ group has at least one fluorinesubstituent. In some embodiments, the R⁷ group is fully fluorinated.

In some embodiments of Formula I(a), the R⁷ substituents on the fusedalicyclic ring on the monomer offer improved solubility of the monomersin water and facilitate polymerization in the presence of thefluorinated acid polymer.

In some embodiments of Formula I(a), m is 2, one R⁷ is sulfonicacid-propylene-ether-methylene and all other R⁷ are hydrogen. In someembodiments, m is 2, one R⁷ is propyl-ether-ethylene and all other R⁷are hydrogen. In some embodiments, m is 2, one R⁷ is methoxy and allother R⁷ are hydrogen. In some embodiments, one R⁷ is sulfonic aciddifluoromethylene ester methylene (—CH₂—O—C(O)—CF₂—SO₃H), and all otherR⁷ are hydrogen.

In some embodiments, pyrrole monomers contemplated for use to form theelectrically conductive polymer in the new composition comprise FormulaII below.

where in Formula II:

-   -   R¹ is independently selected so as to be the same or different        at each occurrence and is selected from hydrogen, alkyl,        alkenyl, alkoxy, alkanoyl, alkythio, aryloxy, alkylthioalkyl,        alkylaryl, arylalkyl, amino, alkylamino, dialkylamino, aryl,        alkylsulfinyl, alkoxyalkyl, alkylsulfonyl, arylthio,        arylsulfinyl, alkoxycarbonyl, arylsulfonyl, acrylic acid,        phosphoric acid, phosphonic acid, halogen, nitro, cyano,        hydroxyl, epoxy, silane, siloxane, alcohol, benzyl, carboxylate,        ether, amidosulfonate, ether carboxylate, ether sulfonate, ester        sulfonate, and urethane; or both R¹ groups together may form an        alkylene or alkenylene chain completing a 3, 4, 5, 6, or        7-membered aromatic or alicyclic ring, which ring may optionally        include one or more divalent nitrogen, sulfur, selenium,        tellurium, or oxygen atoms; and    -   R² is independently selected so as to be the same or different        at each occurrence and is selected from hydrogen, alkyl,        alkenyl, aryl, alkanoyl, alkylthioalkyl, alkylaryl, arylalkyl,        amino, epoxy, silane, siloxane, alcohol, benzyl, carboxylate,        ether, ether carboxylate, ether sulfonate, ester sulfonate, and        urethane.

In some embodiments, R¹ is the same or different at each occurrence andis independently selected from hydrogen, alkyl, alkenyl, alkoxy,cycloalkyl, cycloalkenyl, alcohol, benzyl, carboxylate, ether,amidosulfonate, ether carboxylate, ether sulfonate, ester sulfonate,urethane, epoxy, silane, siloxane, and alkyl substituted with one ormore of sulfonic acid, carboxylic acid, acrylic acid, phosphoric acid,phosphonic acid, halogen, nitro, cyano, hydroxyl, epoxy, silane, orsiloxane moieties.

In some embodiments, R² is selected from hydrogen, alkyl, and alkylsubstituted with one or more of sulfonic acid, carboxylic acid, acrylicacid, phosphoric acid, phosphonic acid, halogen, cyano, hydroxyl, epoxy,silane, or siloxane moieties.

In some embodiments, the pyrrole monomer is unsubstituted and both R¹and R² are hydrogen.

In some embodiments, both R¹ together form a 6- or 7-membered alicyclicring, which is further substituted with a group selected from alkyl,heteroalkyl, alcohol, benzyl, carboxylate, ether, ether carboxylate,ether sulfonate, ester sulfonate, and urethane. These groups can improvethe solubility of the monomer and the resulting polymer. In someembodiments, both R¹ together form a 6- or 7-membered alicyclic ring,which is further substituted with an alkyl group. In some embodiments,both R¹ together form a 6- or 7-membered alicyclic ring, which isfurther substituted with an alkyl group having at least 1 carbon atom.

In some embodiments, both R¹ together form —O—(CHY)_(m)—O—, where m is 2or 3, and Y is the same or different at each occurrence and is selectedfrom hydrogen, alkyl, alcohol, benzyl, carboxylate, amidosulfonate,ether, ether carboxylate, ether sulfonate, ester sulfonate, andurethane. In some embodiments, at least one Y group is not hydrogen. Insome embodiments, at least one Y group is a substituent having Fsubstituted for at least one hydrogen. In some embodiments, at least oneY group is perfluorinated.

In some embodiments, aniline monomers contemplated for use to form theelectrically conductive polymer in the new composition comprise FormulaIII below.

wherein:

-   -   a is 0 or an integer from 1 to 4;    -   b is an integer from 1 to 5, with the proviso that a +b=5; and        R¹ is independently selected so as to be the same or different        at each occurrence and is selected from hydrogen, alkyl,        alkenyl, alkoxy, alkanoyl, alkythio, aryloxy, alkylthioalkyl,        alkylaryl, arylalkyl, amino, alkylamino, dialkylamino, aryl,        alkylsulfinyl, alkoxyalkyl, alkylsulfonyl, arylthio,        arylsulfinyl, alkoxycarbonyl, arylsulfonyl, acrylic acid,        phosphoric acid, phosphonic acid, halogen, nitro, cyano,        hydroxyl, epoxy, silane, siloxane, alcohol, benzyl, carboxylate,        ether, ether carboxylate, amidosulfonate, ether sulfonate, ester        sulfonate, and urethane; or both R¹ groups together may form an        alkylene or alkenylene chain completing a 3, 4, 5, 6, or        7-membered aromatic or alicyclic ring, which ring may optionally        include one or more divalent nitrogen, sulfur or oxygen atoms.

When polymerized, the aniline monomeric unit can have Formula IV(a) orFormula IV(b) shown below, or a combination of both formulae.

where a, b and R¹ are as defined above. In some embodiments, the anilinemonomer is unsubstituted and a=0.

In some embodiments, a is not 0 and at least one R¹ is fluorinated. Insome embodiments, at least one R¹ is perfluorinated.

In some embodiments, fused polycylic heteroaromatic monomerscontemplated for use to form the electrically conductive polymer in thenew composition have two or more fused aromatic rings, at least one ofwhich is heteroaromatic. In some embodiments, the fused polycyclicheteroaromatic monomer has Formula V:

wherein:

-   -   Q is S, Se, Te, or NR⁶;    -   R⁶ is hydrogen or alkyl;    -   R⁸, R⁹, R¹⁰, and R¹¹ are independently selected so as to be the        same or different at each occurrence and are selected from        hydrogen, alkyl, alkenyl, alkoxy, alkanoyl, alkythio, aryloxy,        alkylthioalkyl, alkylaryl, arylalkyl, amino, alkylamino,        dialkylamino, aryl, alkylsulfinyl, alkoxyalkyl, alkylsulfonyl,        arylthio, arylsulfinyl, alkoxycarbonyl, arylsulfonyl, acrylic        acid, phosphoric acid, phosphonic acid, halogen, nitro, nitrile,        cyano, hydroxyl, epoxy, silane, siloxane, alcohol, benzyl,        carboxylate, ether, ether carboxylate, amidosulfonate, ether        sulfonate, ester sulfonate, and urethane; and    -   at least one of R⁸ and R⁹, R⁹ and R¹⁰, and R¹⁰ and R¹¹ together        form an alkenylene chain completing a 5 or 6-membered aromatic        ring, which ring may optionally include one or more divalent        nitrogen, sulfur,selenium, tellurium, or oxygen atoms.

In some embodiments, the fused polycyclic heteroaromatic monomer has aformula selected from the group consisting of Formula V(a), V(b), V(c),V(d), V(e), V(f), V(g), V(h), V(i), V(j), and V(k):

wherein:

-   -   Q is S, Se, Te, or NH; and    -   T is the same or different at each occurrence and is selected        from S, NR⁶, O, SiR⁶ ₂, Se, Te, and PR⁶;    -   Y is N; and    -   R⁶ is hydrogen or alkyl.        The fused polycyclic heteroaromatic monomers may be further        substituted with groups selected from alkyl, heteroalkyl,        alcohol, benzyl, carboxylate, ether, ether carboxylate, ether        sulfonate, ester sulfonate, and urethane. In some embodiments,        the substituent groups are fluorinated. In some embodiments, the        substituent groups are fully fluorinated.

In some embodiments, the fused polycyclic heteroaromatic monomer is athieno(thiophene). Such compounds have been discussed in, for example,Macromolecules, 34, 5746-5747 (2001); and Macromolecules, 35, 7281-7286(2002). In some embodiments, the thieno(thiophene) is selected fromthieno(2,3-b)thiophene, thieno(3,2-b)thiophene, andthieno(3,4-b)thiophene. In some embodiments, the thieno(thiophene)monomer is further substituted with at least one group selected fromalkyl, heteroalkyl, alcohol, benzyl, carboxylate, ether, ethercarboxylate, ether sulfonate, ester sulfonate, and urethane. In someembodiments, the substituent groups are fluorinated. In someembodiments, the substituent groups are fully fluorinated.

In some embodiments, polycyclic heteroaromatic monomers contemplated foruse to form the polymer in the new composition comprise Formula VI:

wherein:

-   -   Q is S, Se, Te, or NR⁶;    -   T is selected from S, NR⁶, O, SiR⁶ ₂, Se, Te, and PR⁶;    -   E is selected from alkenylene, arylene, and heteroarylene;    -   R⁶ is hydrogen or alkyl;        -   R¹² is the same or different at each occurrence and is            selected from hydrogen, alkyl, alkenyl, alkoxy, alkanoyl,            alkythio, aryloxy, alkylthioalkyl, alkylaryl, arylalkyl,            amino, alkylamino, dialkylamino, aryl, alkylsulfinyl,            alkoxyalkyl, alkylsulfonyl, arylthio, arylsulfinyl,            alkoxycarbonyl, arylsulfonyl, acrylic acid, phosphoric acid,            phosphonic acid, halogen, nitro, nitrile, cyano, hydroxyl,            epoxy, silane, siloxane, alcohol, benzyl, carboxylate,            ether, ether carboxylate, amidosulfonate, ether sulfonate,            ester sulfonate, and urethane; or both R¹² groups together            may form an alkylene or alkenylene chain completing a 3, 4,            5, 6, or 7-membered aromatic or alicyclic ring, which ring            may optionally include one or more divalent nitrogen,            sulfur, selenium, tellurium, or oxygen atoms.

In some embodiments, the electrically conductive polymer is a copolymerof a precursor monomer and at least one second monomer. Any type ofsecond monomer can be used, so long as it does not detrimentally affectthe desired properties of the copolymer. In some embodiments, the secondmonomer comprises no more than 50% of the polymer, based on the totalnumber of monomer units. In some embodiments, the second monomercomprises no more than 30%, based on the total number of monomer units.In some embodiments, the second monomer comprises no more than 10%,based on the total number of monomer units.

Exemplary types of second monomers include, but are not limited to,alkenyl, alkynyl, arylene, and heteroarylene. Examples of secondmonomers include, but are not limited to, fluorene, oxadiazole,thiadiazole, benzothiadiazole, phenylenevinylene, phenyleneethynylene,pyridine, diazines, and triazines, all of which may be furthersubstituted.

In some embodiments, the copolymers are made by first forming anintermediate precursor monomer having the structure A-B-C, where A and Crepresent precursor monomers, which can be the same or different, and Brepresents a second monomer. The A-B-C intermediate precursor monomercan be prepared using standard synthetic organic techniques, such asYamamoto, Stille, Grignard metathesis, Suzuki, and Negishi couplings.The copolymer is then formed by oxidative polymerization of theintermediate precursor monomer alone, or with one or more additionalprecursor monomers.

In some embodiments, the electrically conductive polymer is selectedfrom the group consisting of a polythiophene, a polypyrrole, a polymericfused polycyclic heteroaromatic, a copolymer thereof, and combinationsthereof.

In some embodiments, the electrically conductive polymer is selectedfrom the group consisting of poly(3,4-ethylenedioxythiophene),unsubstituted polypyrrole, poly(thieno(2,3-b)thiophene),poly(thieno(3,2-b)thiophene), and poly(thieno(3,4-b)thiophene).

b. Non-Fluorinated Polymeric Acid

Any non-fluorinated polymeric acid, which is capable of doping theconductive polymer, can be used to make new compositions. Any polymerhaving acidic groups with acidic protons can be used. The use of suchacids with conducting polymers such as polythiophenes, polyanilines andpolypyrroles is well known in the art. Examples of acidic groupsinclude, but are not limited to, carboxylic acid groups, sulfonic acidgroups, sulfonimide groups, phosphoric acid groups, phosphonic acidgroups, and combinations thereof. The acidic groups can all be the same,or the polymer may have more than one type of acidic group.

In one embodiment, the acid is a non-fluorinated polymeric sulfonicacid. Some non-limiting examples of the acids are poly(styrenesulfonicacid) (“PSSA”), poly(2-acrylamido-2-methyl-1-propanesulfonic acid)(“PAAMPSA”), and mixtures thereof.

The amount of non-fluorinated polymeric acid present is generally inexcess of that required to counterbalance the charge on the conductingpolymer. In some embodiments, the ratio of acid equivalents ofnon-fluorinated polymeric acid to molar equivalents of conductingpolymer is in the range of 1-5.

The amount of doped conducting polymer in the composite dispersion isgenerally at least 0.1 wt. %, based on the total weight of thedispersion. In some embodiments, the wt. % is from 0.2 to 5.

3. Solvent

The solvent is a high-boiling, polar organic liquid. In someembodiments, the solvent has a boiling point (“b.p.”) of at least 120°C.; in some embodiments, at least 150° C. The solvent is soluble in,miscible with, or dispersible in water. Examples of solvents include,but are not limited to ethylene glycol, dimethlsulfoxide,dimethylacetamide, and N-methylpyrrolidone. Mixtures of solvents mayalso be used.

The solvent is generally present in the composite dispersion in theamount of from 1 to 15 wt. %, based on the total weight of thedispersion; in some embodiments, from 5 to 10 wt. %.

4. Additive

The additive is selected from the group consisting of carbon fullerenes,nanotubes and combinations thereof.

Fullerenes are an allotrope of carbon characterized by a closed-cagestructure consisting of an even number of three-coordinate carbon atomsdevoid of hydrogen atoms. The fullerenes are well known and have beenextensively studied.

Examples of fullerenes include C60, C60-PCMB, and C70, shown below,

as well as C84 and higher fullerenes. Any of the fullerenes may bederivatized with a (3-methoxycarbonyl)-propyl-1-phenyl group (“PCBM”),such as C70-PCBM, C84-PCBM, and higher analogs. Combinations offullerenes can be used.

In some embodiments, the fullerene is selected from the group consistingof C60, C60-PCMB, C70, C70-PCMB, and combinations thereof.

Carbon nanotubes have a cylindrical shape. The nanotubes can besingle-walled or multi-walled. The materials are made by methodsincluding arc discharge, laser ablation, high pressure carbon monoxide,and chemical vapor deposition. The materials are well known andcommercially available. In some embodiments, single-walled nanotubes areused.

The amount of additive present is generally at least 0.2 wt. %, based onthe total weight of the dispersion. The weight ratio of conductivepolymer to additive is generally in the range of 0.5 to 50; in someembodiments, the ratio is 1 to 10.

5. Preparation of the Composite Dispersion

In the following discussion, the doped conductive polymer, solvent, andadditive will be referred to in the singular. However, it is understoodthat more than one of any or all of these may be used.

The new electrically conductive polymer composition is prepared by firstforming the doped conductive polymer and then adding the solvent and theadditive, in any order.

The doped electrically conductive polymer is generally formed byoxidative polymerization of the precursor monomer in the presence of thenon-fluorinated polymeric acid in an aqueous medium. Many of thesematerials are commercially available. The additive can be dispersed inwater or a solvent/water mixture. These mixtures can then be added to anaqueous dispersion of the doped conductive polymer, optionally withadditional solvent.

Alternatively, the additive can be added to the doped conductive polymerdispersion directly as a solid. The solvent can be added to thismixture.

In some embodiments, the pH is increased either prior to the addition ofthe additive or after. The pH can be adjusted by treatment with cationexchange resins, and/or base resins prior to additive addition. In someembodiments, the pH is adjusted by the addition of aqueous basesolution. Cations for the base can be, but are not limited to, alkalimetal, alkaline earth metal, ammonium, and alkylammonium. In someembodiments, alkali metal is preferred over alkaline earth metalcations.

Films made from the composite aqueous dispersions described herein, arehereinafter referred to as “the new films described herein”. The filmscan be made using any liquid deposition technique, including continuousand discontinuous techniques. Continuous deposition techniques, includebut are not limited to, spin coating, gravure coating, curtain coating,dip coating, slot-die coating, spray coating, and continuous nozzlecoating. Discontinuous deposition techniques include, but are notlimited to, ink jet printing, gravure printing, and screen printing.

The films thus formed are smooth, relatively transparent, and can have aconductivity greater than at least 100 S/cm.

7. Buffer Layers

Organic light-emitting diodes (OLEDs) are an organic electronic devicecomprising an organic layer capable of electroluminescence. OLEDs canhave the following configuration:

-   -   anode/buffer layer/EL material/cathode        with additional layers between the electrodes. Electrically        conducting polymers having low conductivity in the range of 10⁻³        to 10⁻⁷ S/cm are commonly used as the buffer layer in direct        contact with an electrically conductive, inorganic oxide anode        such as ITO. However, films of the new compositions having        conductivity greater than 100 S/cm can serve both anode and        buffer layer functions.

In another embodiment of the invention, there are provided buffer layersdeposited from composite aqueous dispersions. The term “buffer layer” or“buffer material” is intended to mean electrically conductive orsemiconductive materials and may have one or more functions in anorganic electronic device, including but not limited to, planarizationof the underlying layer, charge transport and/or charge injectionproperties, scavenging of impurities such as oxygen or metal ions, andother aspects to facilitate or to improve the performance of the organicelectronic device. The term “layer” is used interchangeably with theterm “film” and refers to a coating covering a desired area. The term isnot limited by size. The area can be as large as an entire device or assmall as a specific functional area such as the actual visual display,or as small as a single sub-pixel. Layers and films can be formed by anyconventional deposition technique, including vapor deposition, liquiddeposition (continuous and discontinuous techniques), and thermaltransfer. Continuous deposition techniques, include but are not limitedto, spin coating, gravure coating, curtain coating, dip coating,slot-die coating, spray coating, and continuous nozzle coating.Discontinuous deposition techniques include, but are not limited to, inkjet printing, gravure printing, and screen printing.

8. Electronic Devices

The new films described herein can be used in electronic devices wherethe high conductivity is desired in combination with transparency. Insome embodiments, the films are used as electrodes. In some embodiments,the films are used as transparent conductive coatings.

In another embodiment of the invention, there are provided electronicdevices comprising at least one electroactive layer positioned betweentwo electrical contact layers, wherein the device further includes thenew buffer layer. The term “electroactive” when referring to a layer ormaterial is intended to mean a layer or material that exhibitselectronic or electro-radiative properties. An electroactive layermaterial may emit radiation or exhibit a change in concentration ofelectron-hole pairs when receiving radiation.

As shown in FIG. 1, a typical device, 100, has an anode layer 110, anelectroactive layer 140, and a cathode layer 160. Also shown are threeoptional layers: buffer layer 120; hole transport layer 130; andelectron injection/transport layer 150.

The device may include a support or substrate (not shown) that can beadjacent to the anode layer 110 or the cathode layer 160. Mostfrequently, the support is adjacent to the anode layer 110. The supportcan be flexible or rigid, organic or inorganic. Examples of supportmaterials include, but are not limited to, glass, ceramic, metal, andplastic films.

The anode layer 110 is an electrode that is more efficient for injectingholes compared to the cathode layer 160. The new films of this inventiondescribed herein are particularly suitable as the anode layer because oftheir high conductivity. In some embodiments, they have a conductivityof 100 S/cm or greater. In some embodiments, they have a conductivity of200 S/cm or greater. They are deposited onto substrates using a varietyof techniques well-known to those skilled in the art. Typical depositiontechniques include liquid deposition (continuous and discontinuoustechniques), and thermal transfer.

In some embodiments, the new films described herein are used alone as ananode without optional buffer layer 120. In this embodiment, the newfilms of this invention serve the functions of both anode layer andbuffer layer.

In some embodiments, the new films described herein are used as the toplayer in a bilayer or multilayer anode. The other anode layers caninclude materials containing a metal, mixed metal, alloy, metal oxide ormixed oxide. Suitable materials include the mixed oxides of the Group 2elements (i.e., Be, Mg, Ca, Sr, Ba, Ra), the Group 11 elements, theelements in Groups 4, 5, and 6, and the Group 8-10 transition elements.If the anode layer 110 is to be light transmitting, mixed oxides ofGroups 12, 13 and 14 elements, such as indium-tin-oxide, may be used. Asused herein, the phrase “mixed oxide” refers to oxides having two ormore different cations selected from the Group 2 elements or the Groups12, 13, or 14 elements. Some non-limiting, specific examples ofmaterials for anode layer 110 include, but are not limited to,indium-tin-oxide (“ITO”), indium-zinc-oxide, aluminum-tin-oxide, gold,silver, copper, and nickel. The mixed oxide layer may be formed by achemical or physical vapor deposition process or spin-cast process.Chemical vapor deposition may be performed as a plasma-enhanced chemicalvapor deposition (“PECVD”) or metal organic chemical vapor deposition(“MOCVD”). Physical vapor deposition can include all forms ofsputtering, including ion beam sputtering, as well as e-beam evaporationand resistance evaporation. Specific forms of physical vapor depositioninclude rf magnetron sputtering and inductively-coupled plasma physicalvapor deposition (“IMP-PVD”). These deposition techniques are well knownwithin the semiconductor fabrication arts.

In one embodiment, the mixed oxide layer is patterned. The pattern mayvary as desired. The layers can be formed in a pattern by, for example,positioning a patterned mask or resist on the first flexible compositebarrier structure prior to applying the first electrical contact layermaterial. Alternatively, the layers can be applied as an overall layer(also called blanket deposit) and subsequently patterned using, forexample, a patterned resist layer and wet chemical or dry etchingtechniques. Other processes for patterning that are well known in theart can also be used.

Optional buffer layer 120 may be present adjacent to the anode layer110. The term “buffer layer” or “buffer material” is intended to meanelectrically conductive or semiconductive materials having conductivityusually in the range between 10⁻³ to10⁻⁷ S/cm, but higher conductivitycan be used for some device geometries. The buffer layer may have one ormore functions in an organic electronic device, including but notlimited to, planarization of the underlying layer, charge transportand/or charge injection properties, scavenging of impurities such asoxygen or metal ions, and other aspects to facilitate or to improve theperformance of the organic electronic device.

In some embodiments, the buffer layer 120 comprises the new filmdescribed herein, where the conductivity is 100 S/cm or less.

In some embodiments, optional hole transport layer 130 is present.between anode layer 110 and electroactive layer 140. In someembodiments, optional hole transport layer is present between a bufferlayer 120 and electroactive layer 140. Examples of hole transportmaterials have been summarized for example, in Kirk-Othmer Encyclopediaof Chemical Technology, Fourth Edition, Vol. 18, p. 837-860, 1996, by Y.Wang. Both hole transporting molecules and polymers can be used.Commonly used hole transporting molecules include, but are not limitedto: 4,4′,4″-tris(N,N-diphenyl-amino)-triphenylamine (TDATA);4,4′,4″-tris(N-3-methylphenyl-N-phenyl-amino)-triphenylamine (MTDATA);N,N′-diphenyl-N,N′-bis(3-methylphenyl)-[1,1′-biphenyl]-4,4′-diamine(TPD); 1,1-bis[(di-4-tolylamino) phenyl]cyclohexane (TAPC);N,N′-bis(4-methylphenyl)-N,N′-bis(4-ethylphenyl)-[1,1′-(3,3′-dimethyl)biphenyl]-4,4′-diamine(ETPD); tetrakis-(3-methylphenyl)-N,N,N′,N′-2,5-phenylenediamine (PDA);α-phenyl-4-N,N-diphenylaminostyrene (TPS); p-(diethylamino)benzaldehydediphenylhydrazone (DEH); triphenylamine (TPA);bis[4-(N,N-diethylamino)-2-methylphenyl](4-methylphenyl)methane (MPMP);1-phenyl-3-[p-(diethylamino)styryl]-5-[p-(diethylamino)phenyl]pyrazoline(PPR or DEASP); 1,2-trans-bis(9H-carbazol-9-yl)cyclobutane (DCZB);N,N,N′,N′-tetrakis(4-methylphenyl)-(1,1′-biphenyl)-4,4′-diamine (TTB);N,N′-bis(naphthalen-1-yl)-N,N′-bis-(phenyl)benzidine (α-NPB); andporphyrinic compounds, such as copper phthalocyanine. Commonly used holetransporting polymers include, but are not limited to,polyvinylcarbazole, (phenylmethyl)polysilane, poly(dioxythiophenes),polyanilines, and polypyrroles. It is also possible to obtain holetransporting polymers by doping hole transporting molecules such asthose mentioned above into polymers such as polystyrene andpolycarbonate.

Depending upon the application of the device, the electroactive layer140 can be a light-emitting layer that is activated by an appliedvoltage (such as in a light-emitting diode or light-emittingelectrochemical cell), a layer of material that responds to radiantenergy and generates a signal with or without an applied bias voltage(such as in a photodetector). In one embodiment, the electroactivematerial is an organic electroluminescent (“EL”) material, Any ELmaterial can be used in the devices, including, but not limited to,small molecule organic fluorescent compounds, fluorescent andphosphorescent metal complexes, conjugated polymers, and mixturesthereof. Examples of fluorescent compounds include, but are not limitedto, pyrene, perylene, rubrene, coumarin, derivatives thereof, andmixtures thereof. Examples of metal complexes include, but are notlimited to, metal chelated oxinoid compounds, such astris(8-hydroxyquinolato)aluminum (Alq3); cyclometalated iridium andplatinum electroluminescent compounds, such as complexes of iridium withphenylpyridine, phenylquinoline, or phenylpyrimidine ligands asdisclosed in Petrov et al., U.S. Pat. No. 6,670,645 and Published PCTApplications WO 03/063555 and WO 2004/016710, and organometalliccomplexes described in, for example, Published PCT Applications WO03/008424, WO 03/091688, and WO 03/040257, and mixtures thereof.Electroluminescent emissive layers comprising a charge carrying hostmaterial and a metal complex have been described by Thompson et al., inU.S. Pat. No. 6,303,238, and by Burrows and Thompson in published PCTapplications WO 00/70655 and WO 01/41512. Examples of conjugatedpolymers include, but are not limited to poly(phenylenevinylenes),polyfluorenes, poly(spirobifluorenes), polythiophenes,poly(p-phenylenes), copolymers thereof, and mixtures thereof.

Optional layer 150 can function both to facilitate electroninjection/transport, and can also serve as a confinement layer toprevent quenching reactions at layer interfaces. More specifically,layer 150 may promote electron mobility and reduce the likelihood of aquenching reaction if layers 140 and 160 would otherwise be in directcontact. Examples of materials for optional layer 150 include, but arenot limited to, metal chelated oxinoid compounds, such asbis(2-methyl-8-quinolinolato)(para-phenyl-phenolato)aluminum(III) (BAIQ)and tris(8-hydroxyquinolato)aluminum (Alq₃);tetrakis(8-hydroxyquinolinato)zirconium; azole compounds such as2-(4-biphenylyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole (PBD),3-(4-biphenylyl)-4-phenyl-5-(4-t-butylphenyl)-1,2,4-triazole (TAZ), and1,3,5-tri(phenyl-2-benzimidazole)benzene (TPBI); quinoxaline derivativessuch as 2,3-bis(4-fluorophenyl)quinoxaline; phenanthroline derivativessuch as 9,10-diphenylphenanthroline (DPA) and2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (DDPA); and any one ormore combinations thereof. Alternatively, optional layer 150 may beinorganic and comprise BaO, LiF, Li₂O, or the like.

The cathode layer 160 is an electrode that is particularly efficient forinjecting electrons or negative charge carriers. The cathode layer 160can be any metal or nonmetal having a lower work function than the firstelectrical contact layer (in this case, the anode layer 110). As usedherein, the term “lower work function” is intended to mean a materialhaving a work function no greater than about 4.4 eV. As used herein,“higher work function” is intended to mean a material having a workfunction of at least approximately 4.4 eV.

Materials for the cathode layer can be selected from alkali metals ofGroup 1 (e.g., Li, Na, K, Rb, Cs,), the Group 2 metals (e.g., Mg, Ca,Ba, or the like), the Group 12 metals, the lanthanides (e.g., Ce, Sm,Eu, or the like), and the actinides (e.g., Th, U, or the like).Materials such as aluminum, indium, yttrium, and combinations thereof,may also be used. Specific non-limiting examples of materials for thecathode layer 160 include, but are not limited to, barium, lithium,cerium, cesium, europium, rubidium, yttrium, magnesium, samarium, andalloys and combinations thereof.

The cathode layer 160 is usually formed by a chemical or physical vapordeposition process. In some embodiments, the cathode layer will bepatterned, as discussed above in reference to the anode layer 110.

Other layers in the device can be made of any materials which are knownto be useful in such layers upon consideration of the function to beserved by such layers.

In some embodiments, an encapsulation layer (not shown) is depositedover the contact layer 160 to prevent entry of undesirable components,such as water and oxygen, into the device 100. Such components can havea deleterious effect on the organic layer 140. In one embodiment, theencapsulation layer is a barrier layer or film. In one embodiment, theencapsulation layer is a glass lid.

Though not depicted, it is understood that the device 100 may compriseadditional layers. Other layers that are known in the art or otherwisemay be used. In addition, any of the above-described layers may comprisetwo or more sub-layers or may form a laminar structure. Alternatively,some or all of anode layer 110, the buffer layer 120, the hole transportlayer 130, the electron transport layer 150, cathode layer 160, andother layers may be treated, especially surface treated, to increasecharge carrier transport efficiency or other physical properties of thedevices. The choice of materials for each of the component layers ispreferably determined by balancing the goals of providing a device withhigh device efficiency with device operational lifetime considerations,fabrication time and complexity factors and other considerationsappreciated by persons skilled in the art. It will be appreciated thatdetermining optimal components, component configurations, andcompositional identities would be routine to those of ordinary skill ofin the art.

In one embodiment, the different layers have the following range ofthicknesses: anode 110, 500-5000 Å, in one embodiment 1000-2000 Å;optional buffer layer 120, 50-2000 Å, in one embodiment 200-1000 Å;optional hole transport layer 130, 50-2000 Å, in one embodiment 100-1000Å; photoactive layer 140, 10-2000 Å, in one embodiment 100-1000 Å;optional electron transport layer 150, 50-2000 Å, in one embodiment100-1000 Å; cathode 160, 200-10000 Å, in one embodiment 300-5000 Å. Thelocation of the electron-hole recombination zone in the device, and thusthe emission spectrum of the device, can be affected by the relativethickness of each layer. Thus the thickness of the electron-transportlayer should be chosen so that the electron-hole recombination zone isin the light-emitting layer. The desired ratio of layer thicknesses willdepend on the exact nature of the materials used.

In operation, a voltage from an appropriate power supply (not depicted)is applied to the device 100. Current therefore passes across the layersof the device 100. Electrons enter the organic polymer layer, releasingphotons. In some OLEDs, called active matrix OLED displays, individualdeposits of photoactive organic films may be independently excited bythe passage of current, leading to individual pixels of light emission.In some OLEDs, called passive matrix OLED displays, deposits ofphotoactive organic films may be excited by rows and columns ofelectrical contact layers.

Although methods and materials similar or equivalent to those describedherein can be used in the practice or testing of the present invention,suitable methods and materials are described below. All publications,patent applications, patents, and other references mentioned herein areincorporated by reference in their entirety. In case of conflict, thepresent specification, including definitions, will control. In addition,the materials, methods, and examples are illustrative only and notintended to be limiting.

It is to be appreciated that certain features of the invention whichare, for clarity, described above and below in the context of separateembodiments, may also be provided in combination in a single embodiment.Conversely, various features of the invention that are, for brevity,described in the context of a single embodiment, may also be providedseparately or in any subcombination. Further, reference to values statedin ranges include each and every value within that range.

EXAMPLES A) General Procedure of Film Sample Preparation, Four-ProbeElectrical Resistance Measurement and Calculation of ElectricalConductivity:

One small drop of each dispersion sample was placed on a 3″×1″microscope slide placed on a hot plate set at ˜170° C. in air. Theliquid was spread with a small diameter (˜1 mm) glass rod to form a thinfilm on 2/3 area of the slide as the liquid was evaporating. The slidewas removed from the hot plate and the film was trimmed to a long stripwith a razor blade. Width of the strip ranged from 0.2 cm to 0.7 cm andthe length was about 3 cm. The microscope slide containing the strip wasthen placed on a hot plate set at 210° C. for 10 minutes. Once cooled toroom temperature, silver paste was then painted perpendicular to thelength of the strip to form four electrodes. The two inner parallelelectrodes were about 0.3 cm to 0.5 cm apart and were connected to aKeithley model 616 electrometer for measurement of voltage. The twooutside parallel electrodes were connected to a Keithley model 225Current Supplier. A series of corresponding current/voltage dataobtained at room temperature was recorded to see whether Ohm's law wasfollowed. All the samples in the Examples followed Ohm's law, whichprovided a more or less identical resistance of the correspondingcurrent/voltage data. Once resistance measurement was done, the area inthe two inner electrodes was measured for thickness with a Profilometer.Thickness of the tested films is typically in the range of 1 micrometer(um). Since resistance, thickness, separation length of the two innerelectrodes and the width of the filmstrip are known, electricalconductivity is then calculated. The conductivity unit is expressed as S(Siemens)/cm.

Example 1

This example illustrates preparation and film conductivity of a stableaqueous dispersion containing carbon-nanotubes (CNT), electricallyconducting polymer, and a high boiling organic liquid.

CNT used in this example was HIPco CE608, purchased from CNI (CarbonNanotechnologies, Inc.) at Houston, Tex., USA. HIPco CE608 CNT is singlewall nanotubes, which contains about 3-4% (w/w) residual catalyst. Itwas made by a process using high-pressure carbon monoxide and thenpurified by the Company.

Electrically conducting polymer used in this example ispoly(3,4-ethylenedioxythiophene) doped with non-fluorinated doping acidpoly(styrenesulfonic acid), abbreviated as “PEDOT/PSSA”. PEDOT/PSSA is awell-known electrically conductive polymer. The polymer dispersed inwater is commercially available from H. C. Starck GmbH (Leverkuson,Germany) in several grades under a trade name of Baytron-P. Baytron-PHCV4, one of the commercial aqueous dispersion products, purchased fromStarck was used. The Baytron-P HCV4 sample was determinedgravimetrically to have 1.01% (w/w) solid, which should be PEDOT/PSSA inwater. According to the product brochure, the weight ratio of PEDOT:PSSAis 1:2.5.

Prior to preparation of a CNT composite dispersion, an ethyleneglycol/water solution was prepared. The solution was for reducingPEDOT-PSSA solid % of HCV4, therefore reducing its viscosity. A 19.93%(w/w) ethylene glycol/water solution was made by adding 3.9988 gethylene glycol to 16.0610 g deionized water.

0.0876 g CNT were first placed in a glass jug. To the CNT solids,14.7193 g ethylene glycol (19.93%, w/w)/water solution were added,followed with 13.9081 g Baytron-P HCV4. Based on the quantity of eachcomponent, the mixture contains 0.49% (w/w) PEDOT-PSSA, 10.22% (w/w)ethylene glycol, 0.31% (w/w) CNT, and the remaining is water. Themixture was subjected to sonication for 15 minutes continuously using aBranson Model 450 Sonifier having power set at #4. The glass jug wasimmersed in ice water contained in a tray to remove heat produced fromintense cavitation during entire period of sonication. The mixtureformed a smooth, stable dispersion without any sign of sedimentation. PHof the dispersion was measured to be 2.1 using a pH meter (model 63)from Jenco Electronics, Ltd (San Diego, Calif.).

Films were prepared according to the general procedure described in thinfilm preparation. Thin films are optically transmissive and strongermechanically than those of the conducting polymer without CNT. Thinfilms were tested for electrical conductivity as described in thegeneral procedure. The conductivity of five film samples at roomtemperature was measured to be 509.3 S/cm, 667.3 S/cm, 441.3 S/cm, 546.8S/cm, and 551.2 S/cm.

Example 2

This example illustrates addition of a base solution on stability of thecomposite dispersion prepared in Example 1.

About 10 g of the dispersion sample made in Example 1 was first adjustedto pH3.9 using 0.5N NaOH/water solution first and then 0.1N NaOH/wateras pH got closer to the targeted pH. One half of the pH3.9 dispersionwas further adjusted to pH7.0 with sodium hydroxide/water solution too.Concentration of each component in the dispersions was not significantlyaffected because only a very small amount of base solution was used.Addition of the base solution still maintains homogeneity of thedispersion. There is no sign of sedimentation in both high pHdispersions. The high pH dispersions also form homogeneous films.

Example 3

This example illustrates preparation and film conductivity of a stableaqueous dispersion containing a different carbon nanotube (CNT),electrically conducting polymer, and a high boiling organic liquid.

CNT used in this example was HIPco P0244, also purchased from CNI(Carbon Nanotechnologies, Inc.) at Houston, Tex., USA. HIPco P0244 CNTis single wall nanotubes, which contains about 10% (w/w) residualcatalyst. It was made by a process using high-pressure carbon monoxideand then purified by the Company. Electrically conducting polymer usedin this example is also Baytron-P HCV4. This lot of sample wasdetermined gravimetrically to have 1.1% (w/w) solid, which should bePEDOT/PSSA in water. According to the product brochure, the weight ratioof PEDOT:PSSA is 1:2.5.

Prior to preparation of a CNT composite dispersion, an ethyleneglycol/water solution was prepared. The solution was for reducingPEDOT-PSSA solid % of HCV4, therefore reducing its viscosity. A 18.01%(w/w) ethylene glycol/water solution was made by adding 3.6035 gethylene glycol to 16.4057 g deionized water.

0.0981 g CNT were first placed in a glass jug. To the CNT solids,17.2521 g ethylene glycol (18.01%, w/w)/water solution were added,followed with 15.5701 g Baytron-P HCV4. Based on the quantity of eachcomponent, the mixture contains 0.52% (w/w) PEDOT-PSSA, 9.44% (w/w)ethylene glycol, 0.298% (w/w) CNT, and the remaining is water. Themixture was subjected to sonication for 28 minutes continuously using aBranson Model 450 Sonifier having power set at #4. The glass jug wasimmersed in ice water contained in a tray to remove heat produced fromintense cavitation during entire period of sonication. The mixtureformed a smooth, stable dispersion without any sign of sedimentation. pHof the dispersion was measured to be 2.0 using a pH meter (model 63)from Jenco Electronics, Ltd (San Diego, Calif.).

Films were prepared according to the general procedure described in thinfilm preparation. Thin films are optically transmissive and strongermechanically than those of the conducting polymer without CNT. Thinfilms were tested for electrical conductivity as described in thegeneral procedure. The conductivity of six film samples at roomtemperature was measured to be 608.7 S/cm, 459.3 S/cm, 366.6 S/cm, 528.8S/cm, 481.0 S/cm, and 472.3 S/cm.

Note that not all of the activities described above in the generaldescription or the examples are required, that a portion of a specificactivity may not be required, and that one or more further activitiesmay be performed in addition to those described. Still further, theorder in which activities are listed are not necessarily the order inwhich they are performed.

In the foregoing specification, the concepts have been described withreference to specific embodiments. However, one of ordinary skill in theart appreciates that various modifications and changes can be madewithout departing from the scope of the invention as set forth in theclaims below. Accordingly, the specification and figures are to beregarded in an illustrative rather than a restrictive sense, and allsuch modifications are intended to be included within the scope ofinvention.

Benefits, other advantages, and solutions to problems have beendescribed above with regard to specific embodiments. However, thebenefits, advantages, solutions to problems, and any feature(s) that maycause any benefit, advantage, or solution to occur or become morepronounced are not to be construed as a critical, required, or essentialfeature of any or all the claims.

It is to be appreciated that certain features are, for clarity,described herein in the context of separate embodiments, may also beprovided in combination in a single embodiment. Conversely, variousfeatures that are, for brevity, described in the context of a singleembodiment, may also be provided separately or in any subcombination.

The use of numerical values in the various ranges specified herein isstated as approximations as though the minimum and maximum values withinthe stated ranges were both being preceded by the word “about.” In thismanner slight variations above and below the stated ranges can be usedto achieve substantially the same results as values within the ranges.Also, the disclosure of these ranges is intended as a continuous rangeincluding every value between the minimum and maximum average valuesincluding fractional values that can result when some of components ofone value are mixed with those of different value. Moreover, whenbroader and narrower ranges are disclosed, it is within thecontemplation of this invention to match a minimum value from one rangewith a maximum value from another range and vice versa.

1. An aqueous dispersion comprising: at least one electricallyconductive polymer doped with a non-fluorinated polymeric acid polymer;at least one high-boiling polar solvent, and an additive selected fromthe group consisting of fullerenes, carbon nanotubes, and combinationsthereof.
 2. The dispersion of claim 1, wherein the electricallyconductive polymer is selected from the group consisting ofpoly(selenophenes), poly(tellurophenes), polypyrroles, polyanilines,polycyclic aromatic polymers, copolymers thereof, and combinationsthereof.
 3. The dispersion of claim 2, wherein the electricallyconductive polymer is selected from the group consisting of apolyaniline, a polypyrrole, a polymeric fused polycyclic heteroaromatic,copolymers thereof, and combinations thereof.
 4. The dispersion of claim3, wherein the electrically conductive polymer is selected from thegroup consisting of unsubstituted polyaniline, and unsubstitutedpolypyrrole.
 5. The dispersion of claim 1 wherein the non-fluorinatedpolymeric acid polymer is a polymeric sulfonic acid.
 6. The dispersionof claim 5 wherein the polymeric sulfonic acid is selected from thegroup consisting of poly(styrenesulfonic acid),poly(2-acrylamido-2-methyl-1-propanesulfonic acid) and mixtures thereof.7. The dispersion of claim 1 wherein the amount of doped conductingpolymer in the composite dispersion is in the range of from 0.1% to 5%by weight based on the total weight of the dispersion.
 8. The dispersionof claim 1 wherein an additive is a fullerene.
 9. The dispersion ofclaim 8 wherein the fullerene is selected from the group consisting ofC60, C60-PCMB, C70, C70-PCBM, and combinations thereof.
 10. Thedispersion of claim 1 wherein the amount of additive present is in therange of from 0.2% to 50% by weight based on the total weight of thedispersion.
 11. The dispersion of claim 1 wherein the solvent has aboiling point of at least 120° C.
 12. The dispersion of claim 1 whereinthe solvent is present in the composite dispersion in the range of from1% to 15% by weight based on the total weight of the dispersion.
 13. Thedispersion of claim 1 having a pH greater than
 2. 14. A film made fromthe dispersion of claim
 1. 15. The film of claim 14 having aconductivity of at least 100 S/cm.
 16. An electronic device comprisingat least one layer made from the dispersion of claim
 1. 17. The deviceof claim 16, wherein the layer is an anode.
 18. The device of claim 16,wherein the layer is a buffer layer.
 19. The dispersion of claim 1wherein the at least one polar solvent is selected from the groupconsisting of ethylene glycol, dimethylsulfoxide, dimethylacetamide,N-methylpyrrolidone, and mixtures thereof.
 20. The dispersion of claim 1wherein the fullerene is selected from the group consisting of C60,C60-PCBM, C70, C70-PCBM, and mixtures thereof, the carbon nanotube isHIPco CE608, and mixtures of the nanotube and fullerenes.